EP2496549B1 - Méthacrylates nouveaux non cristallisants, leur fabrication et leur utilisation - Google Patents

Méthacrylates nouveaux non cristallisants, leur fabrication et leur utilisation Download PDF

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EP2496549B1
EP2496549B1 EP10773312.3A EP10773312A EP2496549B1 EP 2496549 B1 EP2496549 B1 EP 2496549B1 EP 10773312 A EP10773312 A EP 10773312A EP 2496549 B1 EP2496549 B1 EP 2496549B1
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methacrylate
holograms
substituted
isocyanate
photopolymer formulation
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EP2496549A2 (fr
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Thomas Fäcke
Friedrich-Karl Bruder
Marc-Stephan Weiser
Thomas RÖLLE
Dennis Hönel
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Bayer Intellectual Property GmbH
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Bayer Intellectual Property GmbH
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C271/06—Esters of carbamic acids
    • C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
    • C07C271/26—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring
    • C07C271/30—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atom of at least one of the carbamate groups bound to a carbon atom of a six-membered aromatic ring to a carbon atom of a six-membered aromatic ring being part of a condensed ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/23—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton
    • C07C323/39—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and nitrogen atoms, not being part of nitro or nitroso groups, bound to the same carbon skeleton at least one of the nitrogen atoms being part of any of the groups, X being a hetero atom, Y being any atom
    • C07C323/43—Y being a hetero atom
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/0005—Production of optical devices or components in so far as characterised by the lithographic processes or materials used therefor
    • G03F7/001—Phase modulating patterns, e.g. refractive index patterns
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/031—Organic compounds not covered by group G03F7/029
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/035—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyurethanes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur

Definitions

  • the invention relates to a novel, non-crystallizing methacrylate and a process for its preparation. Further objects of the invention are a photopolymer formulation comprising the methacrylate according to the invention and the use of the photopolymer formulation for the production of holographic media.
  • Photopolymers are materials which can be exposed by the superposition of two coherent light sources, forming a three-dimensional structure in the photopolymers, which can generally be described by a regional change in the refractive index in the material. Such structures are called holograms, which can also be described as diffractive optical elements. It depends on the specific exposure, which optical functions such a hologram forms.
  • WO 2008/125199 A1 there is described a photopolymer formulation containing polyurethane-based matrix polymers, an acrylate-based writing monomer and photoinitiators.
  • the writing monomer and the photoinitiators are spatially distributed isotropically in the polyurethane matrix.
  • acrylate random monomers described in the PCT application are expensive to produce because they imperatively require a final distillation step to remove the solvent. This is also problematic because it can cause the polymerization of acrylates.
  • R 1 and / or R 2 may comprise 6-24 C atoms, 0-5 S atoms and 0-5 halogen atoms.
  • R 1 and / or R 2 may be substituted with thioether groups, phenyl groups and / or halogen atoms.
  • R 1 and / or R 2 are naphthyl, 3-methylthiophenyl, 2-, 3-, 4-biphenyl, 2-bromophenyl.
  • Another object of the invention is a process for preparing a methacrylate according to the invention, in which an aromatic acid R 2 -COOH is reacted with glycidyl methacrylate and the product is subsequently reacted with an aromatic isocyanate R 1 -NCO.
  • the preparation of the methacrylates according to the invention takes place in a 2-stage synthesis.
  • an acid R 2 -COOH is reacted with glycidyl methacrylate to form a mixture of two alcohols of Reaction Scheme-1.
  • the reaction is typically carried out at 20-180 ° C, preferably at 40-120 ° C and more preferably at 50-100 ° C.
  • Glycidyl methacrylate and a catalyst are charged and the acid is added in portions. Due to the limited solubility, the acid addition is determined by the stirrability of the batch. Progression of the reaction is indicated by the dissolution of the acid. The course of the reaction is controlled by the changing epoxide content. 1 H NMR spectroscopy is particularly suitable as a detection method.
  • the reaction time can be between a few hours to days. Catalysts accelerate the conversion efficiently.
  • Different classes of substances can be used as catalysts: For example. Broensted acids such as phosphoric acid, phosphorous acid, sulfuric acid; Lewis acids such as zinc acetates, zinc acetylacetonates, titanium IV methoxide, tetrakis (dimethylamino) zirconium, Lewis bases such as 2-methylimidazoles, dimethylaminopyridine, borane-pyridine complex, tris (dimethylamino) borane, triphenylphosphine, tris (o-tolyl) phosphine, choline chlorides , Tris (4-dimethyleneaminophenyl) phosphine, tris (4-methoxyphenyl) phosphine, 1,4,5,6-tetrahydropyrimidine, diazabicycloundecane (DABCO) and other amines, and ammonium or
  • the alcohol mixture is urethanized with a monoisocyanate R1-NCO to the methacrylate mixture according to Scheme 2.
  • the urethanization is typically carried out at 20-180 ° C, preferably at 40-120 ° C and more preferably at 50-100 ° C.
  • the alcohol is initially charged as the product of the first stages, if appropriate mixed with a catalyst and then the isocyanate is added dropwise.
  • the reaction is complete when the NCO content has fallen below 1%, preferably below 0.1% by weight.
  • the NCO content can be determined by means of IR spectroscopy or by titration.
  • the preferred method of addition is influenced in this specific case by the handling and thus by the viscosity of the starting materials.
  • the catalysts used for the reaction of the reaction scheme 2 amines and metal compounds of the metals tin, zinc, iron, bismuth, molybdenum, cobalt, calcium, magnesium and zirconium.
  • metal compounds of the metals tin, zinc, iron, bismuth, molybdenum, cobalt, calcium, magnesium and zirconium.
  • lead octoate or tertiary amines such as triethylamine, tributylamine, dimethylbenzylamine, dicyclohexylmethylamine, dimethylcyclohexylamine, N, N, N ', N'-tetramethyl-diamino-diethyl ether, bis (dimethylamino-propyl) -urea, N-methyl or N-ethylmorpholine, N, N'-dimorpholinodiethyl ether (DMDEE), N-cyclohexylmorpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylbutane diamine, N, N, N ', N'-tetramethylhexanediamine-1,6, pentamethyldiethylenetriamine, dimethylpiperazine, N-dimethylaminoethylpiperidine, 1,2-di
  • catalysts here are dibutyltin dilaurate, dimethyltin dicarboxylate, ferric acetylacetonate, 1,4-diazabicyclo [2.2.2] octane, diazabicyclononane, diazabicycloundecane, 1,1,3,3-tetramethylguanidine, 1,3,4,6 , 7,8-hexahydro-1-methyl-2H-pyrimido (1,2-a) pyrimidine.
  • the isocyanates R1-NCO include monoisocyanates, wherein R1 may have the meanings given above.
  • Particularly suitable are the isomeric methylthiophenyl isocyanate, such as 2-methylthiophenyl isocyanate, 3-methylthiophenyl isocyanate, 4-methylthiophenyl isocyanate, bis-, tris-, tetra- and penta (methylthio) phenyl isocyanate, ethylthiophenyl isocyanate, n-propylthiophenyl isocyanate, isopropyl anthiophenyl isocyanate, butylthiophenyl isocyanate, phenylthiophenyl isocyanate, bis (phenylthio) phenyl isocyanate, naphthylthiophenyl isocyanate, biphenyl isocyanate such as 2-biphenyl isocyanate, 3-biphenyl iso
  • phenyl isocyanate mixed substituents on the phenyl isocyanate are possible, e.g. Chlorobromophenyl isocyanate, bromine (methylthio) phenyl isocyanate, methylthio (phenyl) phenyl isocyanate and analogs.
  • Substituted or unsubstituted naphthyl isocyanates are also suitable, such as naphthyl isocyanate, phenyl naphthyl isocyanate, thiomethyl naphthyl isocyanate, thioethyl naphthyl isocyanate, thiopropyl naphthyl isocyanate, bromonaphthyl isocyanate, chloro naphthyl isocyanate, and polysubstituted and mixed substituted naphthyl isocyanates.
  • naphthyl isocyanate such as naphthyl isocyanate, phenyl naphthyl isocyanate, thiomethyl naphthyl isocyanate, thioethyl naphthyl isocyanate, thiopropyl naphthyl isocyanate, bromonaphthyl isocyanate, chloro naphthyl isocyanate, and
  • 2-biphenyl isocyanate 3-biphenyl isocyanate and 4-biphenyl isocyanate, 3-methylthiophenyl isocyanate and Napthylisocyanat.
  • Suitable acids R 2 -COOH are in particular aromatic acids, which may be a substituted benzoic acid or a substituted or unsubstituted naphthylic acid.
  • R2-COOH R2 may have the meanings given above.
  • phenylbenzoic acids such as 2-, 3- and 4-phenylbenzoic acid
  • isomeric bis- and tris- (phenyl) benzoic acids the isomeric naphthylbenzoic acids, chlorobenzoic acid, dichlorobenzoic acid, trichlorobenzoic acid, tetrachlorobenzoic acid, pentachlorobenzoic acid
  • the isomeric bromobenzoic acids dibromobenzoic acid, tribromobenzoic acid, Tetrabromobenzoic acid, pentabromobenzoic acid, methylthiophenylbenzoic acid, 2-methylthiophenylbenzoic acid, 3-methylthiobenzoic acid
  • 4-methylthiobenzoic acid bis-, tris-, tetra- and penta (methylthio) benzoic acid, ethylthiobenzoic acid, n-propylthiobenzoic acid, iso
  • a further subject of the invention is a photopolymer formulation comprising matrix polymers, writing monomers and photoinitiators, the writing monomers comprising a methacrylate according to the invention.
  • Suitable matrix polymers are amorphous thermoplastics such as polyacrylates, polymethyl methacrylates or copolymers of methyl methacrylate, methacrylic acid or other alkyl acrylates and alkyl methacrylates and acrylic acid; Polyvinyl acetate and its partially hydrolyzed derivatives such as polyvinyl alcohols, gelatin, cellulose esters and cellulose ethers such as cellulose acetobutyrate and polyethylene oxides. With particular preference the matrix polymers are polyurethanes.
  • matrix polymers based on a functional binder and a crosslinker are also suitable.
  • two components epoxy systems and urethane systems can be used with two components urethane systems are preferred.
  • the urethane crosslinking one needs a polyisocyanate crosslinker and a hydroxy- or amine-functional binder (resin).
  • Suitable compounds of the polyisocyanate crosslinkers are all aliphatic, cycloaliphatic, aromatic or araliphatic di- and triisocyanates known to the person skilled in the art, it being immaterial whether these were obtained by phosgenation or by phosgene-free processes.
  • the high molecular weight secondary products (oligoisocyanates and polyisocyanates) of monomeric di- and / or triisocyanates with urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, which are well known to the person skilled in the art, may also be used.
  • Uretdione, Iminooxadiazindion Modell each individually or in any mixtures with each other are used.
  • Suitable monomers are di- or triisocyanates, such as butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, isocyanatomethyl-1,8-octane diisocyanate (TIN), 2,4- and / or 2,6-toluene diisocyanate.
  • di- or triisocyanates such as butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), trimethylhexamethylene diisocyanate (TMDI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, isocyanatomethyl-1,8-octane diisocyanate (
  • isocyanate-functional prepolymers having urethane, allophanate or biuret structures as can be obtained in a manner which is in itself well known by reacting the abovementioned di-, tri- or polyisocyanates in excess with hydroxy- or amino-functional compounds. Any unreacted starting isocyanate can then be removed to obtain low-monomer products. To accelerate the formation of prepolymer, it may be helpful to use catalysts which are well known to those skilled in the art from polyurethane chemistry.
  • oligo- and polyisocyanates derived from monomeric diisocyanates with urethane, urea, carbodiimide, acylurea, isocyanurate, allophanate, biuret, oxadiazinetrione, uretdione, iminooxadiazinedione, each of which is used individually or in any desired mixtures with one another become.
  • oligo- and polyisocyanates aliphatic diisocyanates with isocyanurate, allophanate, biuret, uretdione, Iminooxadiazindion Modell, each of which is used individually or in any mixtures with each other.
  • Suitable hydroxy- or amine-functional binders are diols or polyols and / or amines having a number-average molecular weight in the range from 500 to 13000 g / mol, preferably 700 to 8500 g / mol.
  • Preferred resins for this purpose have an average functionality of 1.5 to 3.5, preferably from 1.8 to 3.2, particularly preferably from 1.9 to 3.1.
  • Such polyols of the abovementioned type are, for example, polyester alcohols based on aliphatic, cycloaliphatic and / or aromatic di-, tri- and / or polycarboxylic acids with di-, tri- and / or polyfunctional alcohols and on lactone-based polyester alcohols.
  • Preferred polyester alcohols having a molecular weight preferably from 500 to 4000, more preferably from 650 to 2500 g / mol are e.g. Reaction products of adipic acid with hexanediol, butanediol or neopentyl glycol or mixtures of said diols.
  • polyether polyols which are obtainable by polymerization of cyclic ethers or by reaction of alkylene oxides with a starter molecule.
  • polyethylene and / or polypropylene glycols of a number average molecular weight of 500 to 13000 g / mol, furthermore polytetrahydrofurans of a number average molecular weight of 500 to 8000, preferably from 650 to 3000 g / mol.
  • Preferred polyether polyols are polyethylene / polypropylene glycols having a polypropylene content of at least 70% and a functionality of 1.9 to 3.1.
  • polyester-polyether-polyester block polyols which can be obtained by reacting polyether polyols with lactones.
  • polyester-polyether-polyester block polyols particularly preferably polyester-polyether-polyester block polyols based on polytetrahydrofurans having a number-average molecular weight of from 200 to 2000 g / mol and ⁇ -caprolactone, these polyester-polyether-polyester block polyols have a number average molecular weight of 1000 to 8000 g / mol.
  • hydroxyl-terminated polycarbonates obtained by reacting diols or lactone-modified diols or bisphenols, such as. Bisphenol A, accessible with phosgene or carbonic diesters such as diphenyl carbonate or dimethyl carbonate.
  • Examples which may be mentioned are the polymeric carbonates of 1,6-hexanediol of a number average molecular weight of 500 to 8000 g / mol, and the carbonates of reaction products of 1,6-hexanediol with ⁇ -caprolactone in a molar ratio of 1 to 0.1.
  • Preferred carbonates are the aforementioned polycarbonate diols of a number average molecular weight of 650 to 3000 g / mol based on 1,6-hexanediol and / or carbonates of reaction products of 1,6-hexanediol with ⁇ -caprolactone in a molar ratio of 1 to 0.33.
  • Hydroxyl-terminated polyamide alcohols and hydroxyl-terminated polyacrylate diols e.g. Tegomer® BD 1000 (from Tego GmbH, Essen, Germany) can also be used.
  • polyester-polyether-polyester block polyols based on polytetrahydrofurans having a number average molecular weight of 400 to 1400 g / mol and ⁇ -caprolactone, these polyester-polyether-polyester block polyols having a number average molecular weight of 1500 to 4000 g / mol.
  • Photoinitiators are usually initiators which can be activated by actinic radiation and trigger polymerization of the corresponding polymerizable groups. Photoinitiators are known per se, commercially sold compounds, wherein a distinction is made between unimolecular (type I) and bimolecular (type II) initiators. Furthermore, depending on their chemical nature, these initiators are used for the free-radical, anionic (or), cationic (or mixed) forms of the abovementioned polymerizations.
  • the photoinitiators may preferably comprise an anionic, cationic or neutral dye and a coinitiator.
  • Type I systems for radical photopolymerization are, for example, aromatic ketone compounds, for example benzophenones in combination with tertiary amines, alkylbenzophenones, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), anthrone and halogenated benzophenones or mixtures of the types mentioned.
  • aromatic ketone compounds for example benzophenones in combination with tertiary amines, alkylbenzophenones, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), anthrone and halogenated benzophenones or mixtures of the types mentioned.
  • (type II) initiators such as benzoin and its derivatives, benzil ketals, acylphosphine oxides, for example 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bisacyclophosphine oxides, phenylglyoxylic acid esters, camphorquinone, alpha-aminoalkylphenones, alpha-, alpha-dialkoxyacetophenones, [4- (phenylthio) phenyl] octane-1,2-dione-2- (O-benzoyloxime), differently substituted hexarylbisimidazoles (HABI) with suitable coinitiators such as, for example, mercaptobenzoxazole and also alpha-hydroxyalkylphenones.
  • suitable coinitiators such as, for example, mercaptobenzoxazole and also alpha-hydroxyalkylphenones.
  • Suitable ammonium ammonium borate are, for example, tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinapthylbutylborate, tetramethylammonium triphenylbenzylborate, tetra (n-hexyl) ammonium (sec-butyl) triphenylborate, 1-methyl-3-octylimidazolium dipentyldiphenylborate, tetrabutylammonium tris (4-tert.
  • Suitable dyes include, for example, Neu-Methylene Blue, Thionin, Basic Yellow, Pinacynol Chloride, Rhodamine 6G, Gallocyanine, Ethyl Violet, Victoria Blue R, Celestine Blue, Chinaldin Red, Crystal Violet, Brilliant Green, Astrazon Orange G, Darrow Red, Pyronin Y, Basic Red 29, pyrillium I, safranine O, cyanine and methylene blue, azure A ( Cunningham et al., RadTech'98 North America UV / EB Conference Proceedings, Chicago, Apr. 19-22, 1998 ).
  • the photoinitiators used for anionic polymerization are typically (Type I) systems and are derived from transition metal complexes of the first series.
  • chromium salts such as trans-Cr (NH 3 ) 2 (NCS) 4 - ( Kutal et al, Macromolecules 1991, 24, 6872 ) or ferrocenyl compounds ( Yamaguchi et al. Macromolecules 2000, 33, 1152 ).
  • Another possibility for anionic polymerization is the use of dyes, such as crystal violet leuconitrile or malachite green leuconitrile, which can polymerize cyanoacrylates by photolytic decomposition ( Neckers et al. Macromolecules 2000, 33, 7761 ).
  • the chromophore is incorporated into the polymer, so that the resulting polymers are colored through.
  • the photoinitiators used for the cationic polymerization consist essentially of three classes: aryldiazonium salts, onium salts (in particular: iodonium, sulfonium and selenonium salts) and organometallic compounds.
  • Phenyl diazonium salts can produce a cation upon irradiation, both in the presence and absence of a hydrogen donor, which initiates polymerization.
  • the efficiency of the overall system is determined by the nature of the counterion used to form the diazonium compound. Preference is given here to the less reactive but rather expensive SbF 6 - , AsF 6 - or PF 6 - .
  • sulfonium salts are compounds that decompose according to Norrish (II) ( Crivello et al., Macromolecules, 2000, 33, 825 ).
  • Preferred photoinitiators are mixtures of tetrabutylammonium triphenylhexylborate, tetrabutylammonium triphenylbutylborate, tetrabutylammonium trinapthylbutylborate, tetrabutylammonium tris- (4-tert-butyl) -phenylbutylborate, tetrabutylammonium tris- (3-fluorophenyl) -hexylborate and tetrabutylammonium tris- (3-chloro-4-methylphenyl ) -hexylborate with dyes such as Astrazon Orange G, Methylene Blue, New Methylene Blue, Azure A, Pyrillium I, Safranine O, Cyanine, Gallocyanine, Brilliant Green, Crystal Violet, Ethyl Violet and Thionin.
  • dyes such as Astrazon Orange G, Methylene Blue, New Methylene Blue, Azure A
  • radical stabilizers can also be used in the formulations according to the invention.
  • radical stabilizers are suitable inhibitors and antioxidants as in " Methods of Organic Chemistry "(Houben-Weyl), 4th Edition, Volume XIV / 1, p 433ff, Georg Thieme Verlag, Stuttgart 1961 , are described. Suitable classes are, for example, phenols such as 2,6Di-tert-butyl-4-methylphenol, cresols, hydroquinones, benzyl alcohols such as benzhydrol, possibly also quinones such. B. 2,5-di-tert-butyl quinone, possibly also aromatic amines such as diisopropylamine or phenothiazine. Preferred free radical stabilizers are 2,6-di-tert-butyl-4-methylphenol, phenothiazine and benzhydrol.
  • one or more catalysts can be used. These preferentially catalyze urethane formation. These are generally the same catalysts which are also used in the second reaction stage in the preparation of the methacrylates of the invention (see above).
  • auxiliaries and additives examples include solvents, plasticizers, leveling agents, wetting agents, defoamers or adhesion promoters, but also polyurethanes, thermoplastic polymers, oligomers, further functional groups, such as, for example, Acetals, epoxides, oxetanes, oxazolines, dioxolanes and / or hydrophilic groups, such as e.g. Salts and / or polyethylene oxides, containing compounds.
  • solvents preference is given to using readily volatile solvents having good compatibility with the formulations essential to the invention, for example ethyl acetate, butyl acetate, acetone.
  • plasticizers used are preferably liquids having good release properties, low volatility and high boiling point.
  • Suitable plasticizers are the compounds known in polymer chemistry, such as esters of aromatic acids, for example dibutyl phthalate, Triisononyl trimellitate or diethylene glycol dibenzoate; the alkylsulfonic acid esters of phenol; Esters of aliphatic acids such as diisononyl cyclohexane-1,2-dicarboxylate, acetyltributyl citrate, dibutyl sebacate, adipic acid polyester or dibutyl adipate; Acetic acid esters such as glycerol triacetate, esters of unsaturated acids such as di (2-ethylhexyl) maleate; Esters of phosphoric acid such as tributoxyethyl phosphate; Sulfonamides such as N-butyl-benzenesulfonamide; Mineral oils such as aromatic oils, naphthenic oils
  • the photopolymer formulation may additionally contain urethanes as plasticizers, which urethanes may be substituted in particular with at least one fluorine atom.
  • the urethanes may have the general formula (5) have in which n ⁇ 1 and n ⁇ 8 and R 3 , R 4 , R 5 are hydrogen and / or independently of one another linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radicals, wherein preferably at least one of R 3 , R 4 , R 5 is substituted by at least one fluorine atom and more preferably R 3 is an organic radical having at least one fluorine atom.
  • the writing monomers additionally comprise a multifunctional writing monomer, which may in particular be a multifunctional acrylate.
  • the multifunctional acrylate in particular the general formula (IV) in which n ⁇ 2 and n ⁇ 4 and R 6 , R 7 are hydrogen and / or independently of one another are linear, branched, cyclic or heterocyclic unsubstituted or optionally also substituted by hetero atoms organic radicals.
  • unsaturated compounds such as ⁇ , ⁇ -unsaturated carboxylic acid derivatives such as acrylates, methacrylates, maleinates, fumarates, maleimides, acrylamides, further vinyl ethers, propenyl ethers, allyl ethers and dicyclopentadienyl units containing compounds and olefinically unsaturated compounds such as styrene, ⁇ -methylstyrene, vinyltoluene, olefins such as 1-octene and / or 1-decene, vinyl esters, (meth) acrylonitrile, (meth) acrylamide, methacrylic acid, acrylic acid may be added. Preference is given to acrylates and methacrylates.
  • Acrylates or methacrylates are generally esters of acrylic acid or methacrylic acid.
  • useful acrylates and methacrylates are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, ethoxyethyl acrylate, ethoxyethyl methacrylate, n-butyl acrylate, n-butyl methacrylate, tert-butyl acrylate, tert-butyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, butoxyethyl acrylate, butoxyethyl methacrylate, Lauryl acrylate, lauryl methacrylate, isobornyl acrylate, isobornyl methacrylate, phenyl acrylate, phenyl methacrylate, p
  • Urethane acrylates are understood as meaning compounds having at least one acrylic acid ester group which additionally have at least one urethane bond. It is known that such compounds can be obtained by reacting a hydroxy-functional acrylic ester with an isocyanate-functional compound.
  • Suitable isocyanates are aromatic, araliphatic, aliphatic and cycloaliphatic di-, tri- or polyisocyanates. It is also possible to use mixtures of such di-, tri- or polyisocyanates.
  • suitable di-, tri- or polyisocyanates are butylene diisocyanate, hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 1,8-diisocyanato-4- (isocyanatomethyl) octane, 2,2,4- and / or 2,4,4- Trimethylhexamethylenediisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes and mixtures thereof of any isomer content, isocyanatomethyl-1,8-octanediisocyanate, 1,4-cyclohexylenediisocyanate, the isomeric cyclohexanedimethylened
  • Suitable hydroxy-functional acrylates or methacrylates for the preparation of urethane acrylates are, for example, compounds such as 2-hydroxyethyl (meth) acrylate, polyethylene oxide mono (meth) acrylates, polypropylene oxide mono (meth) acrylates, polyalkylene oxide mono (meth) acrylates, poly ( ⁇ -caprolactone) mono (meth) acrylates such as Tone® M100 (Dow, Schwalbach, DE), 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 3-hydroxy-2,2-dimethylpropyl (meth) acrylate, hydroxypropyl (meth ) acrylate, acrylic acid (2-hydroxy-3-phenoxypropyl), the hydroxy-functional mono-, di- or tetraacrylates of polyhydric alcohols such as trimethylolpropane, glycerol, pentaerythritol, dipentaerythritol, e
  • isocyanate-reactive oligomeric or polymeric unsaturated acrylate and / or methacrylate group-containing compounds are suitable alone or in combination with the aforementioned monomeric compounds.
  • hydroxyl-containing epoxy (meth) acrylates known per se with OH contents of 20 to 300 mg KOH / g or hydroxyl-containing polyurethane (meth) acrylates with OH contents of 20 to 300 mg KOH / g or acrylated polyacrylates with OH Contents of 20 to 300 mg KOH / g and mixtures thereof and mixtures with hydroxyl-containing unsaturated polyesters and mixtures with polyester (meth) acrylates or mixtures of hydroxyl-containing unsaturated polyester with polyester (meth) acrylates.
  • urethane acrylates are obtainable from the reaction of tris (pisocyanatophenyl) thiophosphate and m-methylthiophenyl isocyanate with alcohol-functional acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.
  • Another object of the invention is the use of a photopolymer formulation according to the invention for producing holographic media, which can be processed by appropriate exposure processes for optical applications in the entire visible and near UV range (300-800 nm) to holograms.
  • Visual holograms include all holograms that can be recorded by methods known to those skilled in the art. These include in-line (Gabor) holograms, off-axis holograms, full aperture transfer holograms, white light transmission holograms ("Rainbow holograms”), Denisyuk holograms, off-axis reflection holograms, edge-lit holograms and holographic stereograms, preferred are reflection holograms, denisy holograms, transmission holograms.
  • Possible optical functions of the holograms that can be produced with the photopolymer compositions according to the invention correspond to the optical functions of light elements such as lenses, mirrors, deflecting mirrors, filters, diffusers, diffractive elements, light guides, waveguides, projection screens and / or masks. Frequently, these optical elements exhibit frequency selectivity depending on how the holograms have been exposed and what dimensions the hologram has.
  • holographic images or representations such as personal portraits, biometric representations in security documents, or generally images or image structures for advertising, security labels, trademark protection, branding, labels, design elements, decorations, illustrations, trading cards, can also be produced by the photopolymer compositions of the present invention .
  • Holographic images can have the impression of a three-dimensional image, but they can also represent image sequences, short films or a number of different objects, depending on which angle, with which (even moving) light source, etc., this is illuminated. Due to these diverse design possibilities, holograms, in particular volume holograms, represent an attractive technical solution for the above-mentioned application.
  • the photopolymer formulations can be used in particular as a holographic medium in the form of a film.
  • a layer of a material or composite material transparent to light in the visible spectral range is coated on one or both sides and optionally a cover layer applied to the photopolymer layer (s).
  • Preferred materials or composite materials of the carrier are based on polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate, polyethylene, polypropylene, cellulose acetate, cellulose hydrate, cellulose nitrate, cycloolefin polymers, polystyrene, polyepoxides, polysulfone, cellulose triacetate (CTA), polyamide, polymethyl methacrylate, polyvinyl chloride, polyvinyl butyral or polydicyclopentadiene or mixtures thereof. Most preferably, they are based on PC, PET and CTA. Composite materials may be film laminates or co-extrudates.
  • Preferred composite materials are duplex and triplex films constructed according to one of the schemes A / B, A / B / A or A / B / C.
  • plastic carriers and planar glass plates can be used, which are used in particular for large-scale imaging accurate exposures, eg for holographic lithography [Ng, Willie W .; Hong, Chi Shain; Yariv, Amnon. Holographic interference lithography for integrated optics. IEEE Transactions on Electron Devices (1978), ED-25 (10), 1193-1200. ISSN: 0018-9383 ].
  • the materials or composite materials of the carrier may be unilaterally or bilaterally anti-adhesive, antistatic, hydrophobed or hydrophilated.
  • the modifications mentioned serve on the photopolymer layer side facing the purpose that the photopolymer layer can be detached from the carrier nondestructive.
  • a modification of the side of the carrier facing away from the photopolymer layer serves to ensure that the media according to the invention meet specific mechanical requirements which are required, for example, in processing in roll laminators, in particular in roll-to-roll processes.
  • holographic media which can be produced in this way were subsequently measured by means of a measuring arrangement according to FIG. 1 tested for holographic properties as follows:
  • the beam of a He-Ne laser (emission wavelength 633 nm) was converted into a parallel homogeneous beam by means of the spatial filter (SF) and together with the collimation lens (CL).
  • the final cross sections of the signal and reference beam are defined by the iris diaphragms (I).
  • the diameter of the iris aperture is 0.4 cm.
  • the polarization-dependent beam splitters (PBS) divide the laser beam into two coherent identically polarized beams. Through the ⁇ / 2 plates, the power of the reference beam was set to 0.5 mW and the power of the signal beam to 0.65 mW. The performances were determined with the semiconductor detectors (D) with the sample removed.
  • the angle of incidence ( ⁇ 0 ) of the reference beam is -21.8 °
  • the angle of incidence ( ⁇ 0 ) of the signal beam is 41.8 °.
  • the angles are measured from the sample standard to the beam direction. According to FIG. 1 Therefore, ⁇ 0 has a negative sign and ⁇ 0 has a positive sign.
  • the interference field of the two overlapping beams produced a grid of bright and dark stripes perpendicular to the bisector of the two beams incident on the sample (reflection hologram).
  • the stripe distance A, also called the grating period, in the medium is ⁇ 225 nm (the refractive index of the medium is assumed to be ⁇ 1.504).
  • FIG. 1 shows the holographic experimental setup, with which the diffraction efficiency (DE) of the media was measured.
  • RD reference direction of the turntable.
  • the written holograms have now been read out in the following way.
  • the shutter of the signal beam remained closed.
  • the shutter of the reference beam was open.
  • the iris diaphragm of the reference beam was closed to a diameter ⁇ 1 mm. It was thus achieved that for all rotation angles ( ⁇ ) of the medium, the beam was always located completely in the previously written hologram.
  • the turntable computer controlled the angular range from ⁇ min to ⁇ max with an angle increment of 0.05 °.
  • ⁇ is measured from the sample standard to the reference direction of the turntable.
  • ⁇ 0 -31.8 °.
  • the powers of the beam transmitted in the zeroth order were measured by means of the corresponding detector D and the powers of the beam deflected to the first order by means of the detector D.
  • P D is the power in the detector of the diffracted beam and P T is the power in the detector of the transmitted beam.
  • the Bragg curve was measured, it describes the diffraction efficiency ⁇ as a function of the rotary w ⁇ of the written hologram measured and stored in a computer.
  • the intensity transmitted in the zeroth order was also recorded against the angle of rotation ⁇ and stored in a computer.
  • the maximum diffraction efficiency (DE ⁇ max ) of the hologram, ie its peak value, was determined during ⁇ reconstruction . It may be necessary to change the position of the detector of the diffracted beam to determine this maximum value.
  • the refractive index contrast ⁇ n and the thickness d of the photopolymer layer has now been determined by means of the coupled wave theory (cf. H. Kogelnik, The Bell System Technical Journal, Volume 48, November 1969, Number 9 Page 2909 - Page 2947 ) to the measured Bragg curve and the angle profile of the transmitted intensity. It should be noted that due to the thickness shrinkage occurring due to the photopolymerization, the strip spacing A 'of the hologram and the orientation of the strips (slant) may deviate from the strip spacing A of the interference pattern and its orientation.
  • ⁇ ⁇ 1 1 - 1 - ⁇ / ⁇ 2 sin 2 ⁇ ⁇ 2 - ⁇ 2 .
  • ⁇ is the lattice strength
  • ⁇ is the detuning parameter
  • ⁇ ' is the orientation (slant) of the refractive index lattice that was written.
  • ⁇ 'and ⁇ ' correspond to the angles ⁇ 0 and ⁇ 0 of the interference field when writing the hologram, but measured in the medium and valid for the lattice of the hologram (after thickness shrinkage).
  • n is the average refractive index of the photopolymer and was set to 1,504.
  • ⁇ is the wavelength of the laser light in vacuum.
  • the detector for the diffracted light can detect only a finite angular range, the Bragg curve is not completely detected by wide holes (small d ' ) in a ⁇ -scan, but only the central area, with suitable detector positioning. Therefore, the complementary to the Bragg curve shape of the transmitted intensity to adjust the layer thickness d 'is additionally used.
  • FIG. 2 shows the representation of the Bragg curve ⁇ according to the Coupled Wave Theory (dashed line), the measured diffraction efficiency (filled circles) and the transmitted power (black solid line) against the Winkelduning ⁇ .
  • FIG. 2 shows the measured transmitted power P T (right y -axis) plotted against the angle reading ⁇ , the measured diffraction efficiency ⁇ (left y- axis) plotted as solid circles against the angle detection ⁇ (as far as the finite size of the detector allowed) and the adaptation of the Kogelnik theory as a dashed line (left y-axis).
  • this procedure may be repeated several times for different exposure times t on different media to determine at which average absorbed dose of the incident laser beam is going to saturate upon writing the hologram DE.
  • the powers of the partial beams have been adjusted so that the same power density is achieved in the medium at the angles ⁇ 0 and ⁇ 0 used.
  • Example 1.1-1.3 General manufacturing specification according to Table 1
  • Example 2.1-2.3 General manufacturing specification according to Table 2
  • Example 3.1-3.3 General manufacturing specification according to Table 3
  • Table 1 example product feedstocks reaction conditions description 1.1 1.
  • Example 1.3 60 ° C, 22h High viscosity, slightly cloudy liquid 2.
  • 1.0 mg DBTL 3. 5.0 g of m-methylthiophenyl isocyanate Mixture of 3 - [(2-methylacryloyl) oxy] -2 - [(3-methylthiophenylcarbamoyl) oxy] propylnaphthalenes-1-carboxylate and 2 - [(2-methylacryloyl) oxy] -1 - ⁇ [(3-methylthiophenylcarbamoyl) oxy] methyl ⁇ ethyl naphthalene-1-carboxylate.
  • Example 5.1-5.6 Analogously to the procedure in Example 5.1-5.6, 3.792 g of the polyol from Example 4.0, 2.500 g of the example 3.3.2.500 g of the fluorinated plasticizer from Example 6.0, 0.1 g of CGI-909 (tetrabutylammonium tris (3-chloro-4-methylphenyl) (hexyl) borate), 0.015 g of glass beads of size 20 microns, 0.01 g of fresh methylene blue at 60 ° C and 0.345 g of N-ethylpyrilidone mixed so that a clear solution was obtained. It was then cooled to 30 ° C, 0.702 g Desmodur ® XP 2410 added and mixed again.
  • CGI-909 tetrabutylammonium tris (3-chloro-4-methylphenyl) (hexyl) borate
  • the holographic media according to the invention have a good holographic performance.
  • the index modulation is between 0.0026 and 0.0265.
  • the preparation of the methacrylates according to the invention (Examples 1.1-3.3) can be carried out easily; in particular, no distillation step is necessary.

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Claims (13)

  1. Méthacrylate de formule générale (I) ou (II) et leurs mélanges
    Figure imgb0044
     caractérisé en ce que R1 et R2 sont indépendamment l'un de l'autre des radicaux phényle substitués, naphtyle substitués et/ou non substitués.
  2. Méthacrylate selon la revendication 1, caractérisé en ce que R1 et/ou R2 comprennent 6 à 24 atomes C, 0 à 5 atomes S et 0 à 5 atomes d'halogène.
  3. Méthacrylate selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que R1 et/ou R2 sont substitués avec des groupes thioéther, des groupes phényle et/ou des atomes d'halogène.
  4. Méthacrylate selon l'une quelconque des revendications 1 à 3, caractérisé en ce que R1 et/ou R2 représentent naphtyle, 3-méthylthiophényle, 2-, 3-, 4-biphényle, 2-bromophényle.
  5. Procédé de fabrication d'un méthacrylate selon la revendication 1, caractérisé en ce qu'un acide aromatique R2-COOH est mis en réaction avec du méthacrylate de glycidyle, puis le produit est mis en réaction avec un isocyanate aromatique R1-NCO.
  6. Formulation de photopolymère comprenant des polymères de matrice, des monomères d'écriture et des photoinitiateurs, caractérisée en ce que les monomères d'écriture contiennent un méthacrylate selon l'une quelconque des revendications 1 à 4.
  7. Formulation de photopolymère selon la revendication 6, caractérisée en ce que les polymères de matrice sont des polyuréthanes.
  8. Formulation de photopolymère selon l'une quelconque des revendications 6 ou 7, caractérisée en ce que les photoinitiateurs comprennent un colorant anionique, cationique ou neutre et un co-initiateur.
  9. Formulation de photopolymère selon l'une quelconque des revendications 6 à 8, caractérisée en ce qu'elle contient également des uréthanes en tant que plastifiants, les uréthanes pouvant notamment être substitués avec au moins un atome de fluor.
  10. Formulation de photopolymère selon la revendication 9, caractérisée en ce que les uréthanes ont la formule générale (III)
    Figure imgb0045
     dans laquelle n ≥ 1 et n ≤ 8, et R3, R4, R5 représentent l'hydrogène et/ou, indépendamment les uns des autres, des radicaux organiques linéaires, ramifiés, cycliques ou hétérocycliques non substitués ou éventuellement également substitués avec des hétéroatomes, au moins un des radicaux R3, R4, R5 étant de préférence substitué avec au moins un atome de fluor et R3 étant de manière particulièrement préférée un radical organique comprenant au moins un atome de fluor.
  11. Formulation de photopolymère selon l'une quelconque des revendications 5 à 10, caractérisée en ce que les monomères d'écriture comprennent également un monomère d'écriture multifonctionnel, celui-ci pouvant notamment être un acrylate multifonctionnel.
  12. Formulation de photopolymère selon la revendication 11, caractérisée en ce que l'acrylate multifonctionnel a la formule générale (IV)
    Figure imgb0046
     dans laquelle n ≥ 2 et n ≤ 4, et R6, R7 représentent l'hydrogène et/ou, indépendamment les uns des autres, des radicaux organiques linéaires, ramifiés, cycliques ou hétérocycliques non substitués ou éventuellement également substitués avec des hétéroatomes.
  13. Utilisation d'une formulation de photopolymère selon l'une quelconque des revendications 6 à 12 pour la fabrication de matériaux holographiques, notamment pour la fabrication d'hologrammes directs, d'hologrammes indirects, d'hologrammes de transfert à pleine ouverture, d'hologrammes en lumière blanche, d'hologrammes Denisyuk, d'hologrammes indirects par réflexion, d'hologrammes lumineux et de stéréogrammes holographiques.
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TWI506018B (zh) 2015-11-01
CN104892462A (zh) 2015-09-09
TW201130796A (en) 2011-09-16
JP2013510116A (ja) 2013-03-21
US20120219885A1 (en) 2012-08-30
JP5793147B2 (ja) 2015-10-14
KR101767280B1 (ko) 2017-08-23
CN102666469A (zh) 2012-09-12
WO2011054818A2 (fr) 2011-05-12
EP2496549A2 (fr) 2012-09-12
CN102666469B (zh) 2016-03-02
KR20120099426A (ko) 2012-09-10
WO2011054818A3 (fr) 2011-09-15
CN104892462B (zh) 2017-08-22

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